Low vaporizable ethylenically unsaturated monomer emission vinyl ester and polyester resin compositions

ABSTRACT

Vinyl ester or polyester resins containing polymerizable, vaporizable, ethylenically unsaturated monomers and an emission suppressing amount of ceresin wax is improved with the addition of a drying oil such as corn oil and an epoxidized drying oil such as epoxidized soybean oil. The improvement is in secondary adhesion. The compositions are useful in the preparation of coating and laminates.

FIELD OF THE INVENTION

The present invention concerns low styrene emission vinyl ester andpolyester formulations containing ceresin wax as a styrene emissiondepressant and drying oil and epoxidized drying oil as secondaryadhesion promoters.

BACKGROUND OF THE INVENTION

Most vinyl ester resins and unsaturated polyester resins containpolymerizable, vaporizable, ethylenically unsaturated monomers such asstyrene as a reactive diluent. Since styrene or other polymerizable,vaporizable, ethylenically unsaturated monomer is a volatile componentwhich tends to be released to the atmosphere during storage and/orcuring of the thermosettable vinyl ester and unsaturated polyesterresins, it is becoming more and more desirable to reduce the level ofstyrene or other polymerizable, vaporizable monomer which is released tothe atmosphere during storage and/or cure. One method for reducing therelease of styrene or other polymerizable, vaporizable monomer into theatmosphere is to include ceresin wax in the formulation. While this doesindeed reduce the amount of styrene released into the atmosphere, thecomposition suffers from a loss in secondary adhesion. It wouldtherefore be highly desirable and beneficial to incorporate into theformulation components which will eliminate or decrease the loss insecondary adhesion.

It has now been discovered that the loss in secondary adhesion frompolymerizable, vaporizable, ethylenically unsaturated monomer such asstyrene containing vinyl ester and unsaturated polyester formulationscontaining ceresin wax as a polymerizable, vaporizable, ethylenicallyunsaturated monomer emission suppressant can be accomplished byincorporating into the formulation a combination of corn oil andepoxidized soybean oil.

SUMMARY OF THE INVENTION

The present invention concerns an improvement in vinyl ester andunsaturated polyester resin compositions containing a polymerizable,vaporizable, ethylenically unsaturated monomer and a polymerizable,ethylenically unsaturated monomer emission suppression amount of ceresinwax: which improvement comprises employing in said compositions asecondary adhesion promoting amount of at least one drying oil and atleast one epoxidized drying oil.

Another aspect of the present invention pertains to a polymlerizable,vaporizable, ethylenically unsaturated vinyl monomersuppressant/secondary adhesion promoter additive composition comprising(1) at least one vaporizable ethylenically unsaturated monomer, (2)ceresin wax, (3) at least one drying oil, and (4) at least oneepoxidized drying oil.

Another aspect of the present invention pertains to a curablecomposition comprising (A) at least one vinyl ester resin or at leastone unsaturated polyester resin or a combination thereof; (B) at leastone polymerizable, vaporizable, ethylenically unsaturated monomer; (C) apolymerizable, ethylenically unsaturated monomer emission suppressionamount of ceresin wax; (D) a secondary adhesion promotion amount of atleast one drying oil; (E) a secondary adhesion promotion amount of atleast one epoxidized drying oil: and (F) a curing amount of a suitablecuring agent.

A further aspect of the present invention pertains to a substratematerial saturated or impregnated with the aforementioned curablecomposition.

A further aspect of the present invention pertains to the product orarticle resulting from shaping one or more plies of the aforementionedsaturated or impregnated substrate material into a desired configurationand curing.

The present invention may suitably comprise, consist of, or consistessentially of, the aforementioned components.

The invention illustratively disclosed herein may suitably be practicedin the absence of any component which is not specifically disclosed orenumerated herein.

DETAILED DESCRIPTION OF THE INVENTION Additive Composition

The vaporizable ethylenically unsaturated vinyl monomersuppressant/secondary adhesion promoter additive composition of thepresent invention usually comprises (1) from about 20% to about 40%,preferably from about 20% to about 35%, more preferably from about 25%to about 35% percent by weight of at least one vaporizable ethylenicallyunsaturated monomer, (2) from about 10% to about 25%, preferably fromabout 10% to about 20%, more preferably from about 13% to about 17%percent by weight ceresin wax, (3) from about 10% to about 30%,preferably from about 18% to about 28%, more preferably from about 20%to about 26% percent by weight of at least one drying oil, and (4) fromabout 20% to about 40%, preferably from about 20% to about 35%, morepreferably from about 25% to about 35% percent by weight of at least oneepoxidized drying oil.

Vinyl Ester Resins

Suitable vinyl ester resins which can be employed herein include anysuch resin prepared by the reaction of an epoxy resin having an averageof more than one vicinal epoxy group per molecule with an unsaturatedcarboxylic acid. The reactants are usually employed in amounts whichprovide a ratio of acid groups per epoxy group of from about 0.95:1 toabout 1.05:1, preferably from about 1:1.

Suitable epoxy resins include those which contain an average of morethan one glycidyl group per molecule such as for example glycidylderivatives of aliphatic, cycloaliphatic or aromatic compoundscontaining an average of more than one hydroxyl, carboxyl or amine groupper molecule or any combination thereof and the like. Particularlysuitable such epoxy resins include, for example, the glycidyl ethers ofresorcinol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenolK, fluorene, phenol- or cresol-aldehyde resins, halogenated,particularly bromine substituted derivatives thereof, or any combinationthereof and the like.

Suitable unsaturated carboxylic acids which can be employed in thepreparation of the vinyl ester resins include, for example, acrylicacid, methacrylic acid, glacial methacrylic acid, or any combinationthereof and the like.

The reaction between the epoxy resin and the unsaturated acid is usuallyconducted at temperatures of from about 90° C. to about 130° C.,preferably from about 100° C. to about 120° C., more preferably fromabout 105° C. to about 115° C. for a time sufficient to complete thereaction. The reaction is usually considered complete when the percentacid has reached a value of 1. The reaction time is usually from about 3to about 6 hours.

If desired, a catalyst for promoting the reaction between the epoxyresin and the unsaturated acid can be employed. Suitable such catalystsinclude, tris(dimethylaminomethyl)phenol, tetraethyl ammonium bromide,or any combination thereof and the like. Particularly suitable suchcatalysts include, for example, or any combination thereof and the like.Particularly suitable such catalysts include, for exampletris(dimethylaminomethyl)phenol, or any combination thereof and thelike. The catalysts are usually employed in amounts of from about 0.05to about 0.08, preferably from about 0.055 to about 0.075, morepreferably from about 0.065 parts of catalyst per 100 parts of resultantmixture of the carboxylic acid and epoxy resin.

Unsaturated Polyester Resins

Suitable unsaturated polyester resins which can be employed hereininclude, for example, those prepared by reacting a compound having anaverage of more than one, preferably about two, aliphatic,cycloaliphatic or aromatic hydroxyl groups per molecule with a compoundhaving an average of more than one aliphatic, cycloaliphatic or aromaticcarboxyl groups per molecule, with the proviso that there be present atleast one reactant which contains polymerizable unsaturated groups. Thereactants are usually employed in amounts which provide a ratio of acidgroups per hydroxyl group.

Particularly suitable compounds containing an average of more than onehydroxyl group per molecule from which unsaturated polyester resins canbe prepared include, for example, those compounds having aliphatic,cycloaliphatic or aromatic hydroxyl groups. Particularly suitable suchcompounds include, for example propylene glycol, ethylene glycol,bisphenol A, or any combination thereof and the like.

Suitable compounds containing an average of more than one carboxylicacid group per molecule from which unsaturated polyester resins can beprepared include, for example, fumaric acid, maleic anhydride, succinicanhydride, chlorendic anhydride, orthophthalic acid or anhydrideisophthalic acid or anhydride, terephthalic acid or anhydride, or anycombination thereof and the like.

The reaction between the hydroxyl containing compound and the acid isusually conducted at temperatures of from about 150° C. to about 190°C., preferably from about 170° C. to about 190° C., more preferably fromabout 175° C. to about 185° C. for a time sufficient to complete thereaction. The reaction is usually considered complete when the acidnumber has reached a value of 50 or below. The reaction time is 6 toabout 16 hours.

If desired, a catalyst for promoting the reaction between thehydroxyl-containing compound and the catalyst can be employed. Suitablesuch catalysts include, butyl stannoic acid, para-toluene sulfonic acid,or any combination thereof and the like. Particularly suitable suchcatalysts include, for example butyl stannoic acid, or any combinationthereof and the like. The catalysts are usually employed in amounts offrom about 0.05 to about 1.0, preferably from about 0.05 to about 0.1,more preferably from about 0.075 parts of catalyst per 100 partsresultant mixture of carboxylic acid and hydroxyl containing compound.

Polymerizable, vaporizable ethylenically unsaturated monomers

Suitable polymerizable, vaporizable, ethylenically unsaturated monomerswhich can be employed herein include, for example, styrene, alpha-methylstyrene, chlorostyrene, vinyl benzene, vinyl toluene, p-methylstyrene,divinylbenzene, or any combination thereof and the like. Also suitableare the C₁ -C₈ alkyl esters of acrylic and methacrylic acid. Styrene isthe preferred polymerizable, vaporizable, ethylenically unsaturatedvinyl monomer.

The polymerizable, vaporizable, ethylenically unsaturated monomers areusually employed in amounts of from about 20 to about 60, preferablyfrom about 35 to about 55, more preferably from about 40 to about 50percent by weight based upon the combined weight of the resin and thepolymerizable, vaporizable, ethylenically unsaturated monomer.

Ceresin Wax

Ceresin wax employed herein is a mixture of hydrocarbons of complexcomposition purified by treatment with concentrated sulfuric acid andfiltered through boneblack having a melting point of 61° C. to 78° C.Other names for ceresin wax are: ozokerite wax 170-D, ozokerite wax 170M.B., white ozokerite wax, yellow ozokerite wax, yellow ozokerite wax Sspecial, S&P ozokerite wax yellow, etc. Strahl & Pitsch Inc., a producerof ceresin wax, defines ozokerite as a hydrocarbon wax derived frommineral or petroleum sources.

The ceresin wax is employed in any amount which will suppress emissionof styrene or other volatile polymerizable ethylenically unsaturatedmonomers contained in the formulation during storage and curing.Particularly suitable amounts of ceresin wax include, for example, fromabout 0.15% to about 0.4%, preferably from about 0.15% to about 0.3%,more preferably from about 0.18% to about 0.25 percent by weight basedupon the combined weight of the styrene (polymerizable ethylenicallyunsaturated monomer), any other reactive diluent (polymerizableethylenically unsaturated monomer) which may be present, and resin.

Drying Oil

The term "drying oil" as employed herein means any naturally occurringoil which contains glycerides of linoleic and/or linolenic acids.Suitable drying oils will have an Iodine value of from about 100 toabout 210, preferably from about 115 to about 150, more preferably fromabout 115 to about 140. Particularly suitable such drying oils include,for example, corn oil, linseed oil, safflower oil, soybean oil,sunflower oil, cottonseed oil, rapeseed oil, perilla oil, hempseed oil,or any combination thereof and the like. Corn oil and soybean oil arepreferred.

The drying oil is employed in any amount which in combination with theepoxidized drying oil will enhance the secondary adhesion of theformulation. Particularly suitable amounts of drying oil include, forexample, from about 0.1% to about 0.7, preferably from about 0.2% toabout 0.5%, more preferably from about 0.25% to about 0.4% percent byweight based upon the combined weight of the styrene (polymerizableethylenically unsaturated monomer), any other reactive diluent(polymerizable ethylenically unsaturated monomer) which may be present,and resin.

Epoxidized Drying Oil

The term "epoxidized drying oil" includes any naturally occurring oilswhich contains glycerides of linoleic and or linolenic acids and whichhave been epoxidized. Suitable such epoxidized drying oils include, forexample, epoxidized soybean oil, epoxidized corn oil, epoxidized linseedoil, epoxidized safflower oil, epoxidized sunflower oil, epoxidizedcottonseed oil, epoxidized rapeseed oil, epoxidized perilla oil,epoxidized hempseed oil, or any combination thereof and the like.Epoxidized soybean oil and epoxidized corn oil are preferred.

The epoxidized drying oils can be prepared by reacting an epihalohydrinwith the desired drying oil and then dehydrohalogenating the resultanthalohydrin intermediate with a suitable basic-acting compound such as,for example, an alkali metal halide, alkali metal carbonate and thelike. Sodium hydroxide is preferred. Several epoxidized drying oils areavailable commercially such as, for example epoxidized soybean oil isavailable from Atochem North America as VIKOFLEX 7170, epoxidizedLinseed Oil is available from Atochem North America as VIKOFLEX 7190.

The epoxidized drying oil is employed in any amount which in combinationwith the drying oil will enhance the secondary adhesion of theformulation and retard styrene volatilization some. Particularlysuitable amounts of epoxidized drying oil include, for example, fromabout 0.2 to about 0.7, preferably from about 0.3 to about 0.6, morepreferably from about 0.35 to about 0.55 percent by weight based uponthe combined weight of the styrene (polymerizable ethylenicallyunsaturated monomer), any other reactive diluent (polymerizableethylenically unsaturated monomer) which may be present, and resin.

Curing Agents and Accelerators or Promoters

The compositions of the present invention can be cured by any meanssuitable for curing vinyl ester resins and unsaturated polyester resins.They can be suitably cured by means of azo compounds, peroxides, or anycombination thereof and the like. Particularly suitable curing agentsinclude, for example, methyl ethyl ketone peroxide, cumenehydroperoxide, benzoyl peroxide, or any combination thereof and thelike.

The curing catalysts are usually employed in amounts of from about 1 toabout 2.5, preferably from about 1 to about 1.5, more preferably fromabout 1 to about 1.25 percent by weight based upon the weight of theresin.

Also, if desired, curing accelerators or promoters can be employed.Suitable such curing accelerators or promoters include, for example,cobalt naphthenate, cobalt octoate, N,N-dimethylaniline,N,N-dimethylacetoacetamide, or any combination thereof and the like.

The curing accelerators or promoters are usually employed in amounts offrom about 0.05 to about 0.6, preferably from about 0.1 to about 0.4,more preferably from about 0.1 to about 0.3 percent by weight based uponthe weight of the resin.

Substrate Materials

Suitable substrate materials which can be saturated or impregnated withthe curable compositions of the present invention include natural orsynthetic fibers in woven, mat or multifilament strand form. Suitablesuch materials can be nylon, rayon, cotton, glass, graphite, carbon,aramid, polyester, or any combination thereof and the like.

Other additives can be added to the compositions of the presentinvention such as, for example, pigments, dyes, fillers, or anycombination thereof and the like.

The curable compositions are useful in the preparation of laminates,coatings, polymer concrete and the like.

The following components are employed in the examples and comparativeexperiments.

Vinyl Ester Resin (VER) A is a vinyl ester resin prepared from adiglycidyl ether of bisphenol A having an epoxide equivalent weight of380 to 420 and methacrylic acid in an equivalent ratio of acid per epoxygroup of 1:1. The resin contains 45 percent styrene by weight.

Polyester Resin (PER) A is a rigid, low reactivity, low viscosity,thixotropic, orthophthalic laminating resin commercially available fromReichhold as POLYLITE™ Polyester Resin 33-087. The resin is prepromotedfor room temperature curing with the addition of methyl ethyl ketoneperoxide. The resin contains 43-47 percent styrene by weight.

The following tests are performed on the vinyl ester and/or unsaturatedpolyester compositions.

ETHYLENICALLY UNSATURATED MONOMER EMISSIONS

The test is based on a completely catalyzed, curable, system since it isunder curing conditions that most of the volatile ethylenicallyunsaturated monomer is lost.

The temperature and relative humidity conditions at which the test isconducted is recorded. 100+/-0.5 grams of catalyzed resin is poured intoa tared one gallon (3.78 1) paint can lid having an opened paper clipand the ethylenically unsaturated monomer emissions measured by theweight loss as the resin formulation gels and up to one hour after thegel time. The gel time is determined by raising the paper clip from theresin periodically until the resin tears or sticks to the paper clip.The ethylenically unsaturated monomer loss is reported in g/m² and isdetermined by multiplying the gram weight loss by the factor 60.56. Thefactor is given in the procedure from the California South Coast AirQuality Board.

SECONDARY ADHESION

The secondary adhesion promotion test is a cycle flexing test conductedon cured laminates at 70% of the flexural strength determined by ASTM D790-86. The secondary adhesion test is determined by ASTM D 3479-76(82).

The primary laminate is prepared by saturating 6"×12" glass layers inthe following sequence, CSM/Wr/CSM/Wr/DXM. All layers are thoroughly wetwith resin, but the surface of the last layer of chopped strand mat isnot excessively resin rich. The last chopped strand mat layer is allowedto wet out almost entirely from the addition of resin on the precedingmat layer. (If the layer of chopped strand mat in the initial lay-up isexcessively resin rich, satisfactory secondary adhesion may not beachieved. Too high of an amount of ceresin wax per surface area maydevelop, which the secondary adhesion promoter may not overcome. A resinrich surface is not as structurally sound as one that contains theappropriate amount of glass near the surface.) The five-ply laminate isthen cured at a temperature of approximately 25° C. for 20-24 hours.

The secondary laminate is then prepared on top of the primary laminateby saturating 6"×12" glass layer in the following sequence, CSM/Wr/CSM.

CSM=1.5 oz. chopped strand mat

Wr=24 oz. wovening roving.

The secondary laminate is then cured at a temperature of approximately25° C. for at least 20-24 hours. The resultant cured laminate is thensubjected to the aforementioned ASTM tests.

EXAMPLE 1

Several formulations are tested for styrene emission and secondaryadhesion. The composition and test results are given in Table I.

                                      TABLE I                                     __________________________________________________________________________                 Formulation                                                                   A*   B*   C*   D*   E*   F*   G*   H*   I    J                   __________________________________________________________________________    Resin Type   VER A                                                                              VER A                                                                              VER A                                                                              VER A                                                                              VER A                                                                              VER A                                                                              VER A                                                                              VER A                                                                              VER                                                                                VER A               Styrene content, %.sup.a                                                                   45   45   45   45   45   45   45   45   45   45                  MEK peroxide, %.sup.b                                                                      1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25                Co Nap.sup.d, percent.sup.b                                                                0.3  0.3  0.3  0.3  0.3  0.3  0.3  0.3  0.3  0.3                 Ceresin Wax, %.sup.b                                                                       0    0    0.2  0.2  0.2  0.2  0.2  0.2  0.2  0.2                 Corn oil, %.sup.b                                                                          0    0    0    0    0.7  0.7  0    0    0.3  0.3                 ESO.sup.c, %.sup.b                                                                         0    0    0    0    0    0    0.7  0.7  0.4  0.4                 Temp.,                                                                        °F.   78   70-74                                                                              74   70-71                                                                              74-76                                                                              76-78                                                                              80-81                                                                              78-79                                                                              73-74                                                                              74-75               °C.   25.6 21.1-23.3                                                                          23.3 21.1-21.7                                                                          23.3-24.4                                                                          24.4-25.6                                                                          26.7-27.2                                                                          25.6-26.1                                                                          22.8-23.3                                                                          23.3-23.9           Relative Humidity, %                                                                       56   60-63                                                                              86   56-61                                                                              60-62                                                                              68-76                                                                              62-66                                                                              70-76                                                                              60-62                                                                              62- 64              Styrene loss, g/m.sup.2                                                                    157  213  35   51.5 98.42                                                                              98.69                                                                              61.1 79.9 46   76                  Secondary Adhesion,                                                                        21,680                                                                             --   8,460                                                                              --   11,540                                                                             --   11,680                                                                             --   24,580                                                                             --                  Cycles.sup.e                                                                  __________________________________________________________________________                 Formulation                                                                   K*   L*   M*   N*   O*   P*   Q*   R*   S    T                   __________________________________________________________________________    Resin Type   PER A                                                                              PER A                                                                              PER A                                                                              PER A                                                                              PER A                                                                              PER A                                                                              PER A                                                                              PER A                                                                              PER                                                                                PER A               Styrene content, %.sup.a                                                                   43-47                                                                              43-47                                                                              43-47                                                                              43-47                                                                              43-47                                                                              43-47                                                                              43-47                                                                              43-47                                                                              43-47                                                                              43-47               MEK peroxide, %.sup.b                                                                      1.5  1.5  1.5  1.5  1.5  1.5  1.5  1.5  1.5  1.5                 Co Nap.sup.d, percent.sup.b                                                                --   --   --   --   --   --   --   --   --   --                  Ceresin Wax, %.sup.b                                                                       0    0    0.2  0.2  0.2  0.2  0.2  0.2  0.2  0.2                 Corn oil, %.sup.b                                                                          0    0    0    0    0.7  0.7  0    0    0.3  0.3                 ESO.sup.c, %.sup.b                                                                         0    0    0    0    0    0    0.7  0.7  0.4  0.4                 Temp.,                                                                        °F.   73   74-76                                                                              71-72                                                                              71-72                                                                              72   72   71-72                                                                              71-72                                                                              72   72                  °C.   22.8 23.3-24.4                                                                          21.7-22.2                                                                          21.7-22.2                                                                          22.2 22.2 21.7-22.2                                                                          21.7-22.2                                                                          22.2 22.2                Relative Humidity, %                                                                       66-75                                                                              74-76                                                                              52-56                                                                              54-57                                                                              58-62                                                                              58-62                                                                              53-55                                                                              52-55                                                                              59-63                                                                              59-63               Styrene loss, g/m.sup.2                                                                    163.5                                                                              156.2                                                                              54.5 55.1 89   92.6 43.6 41.8 26   38.1                Secondary Adhesion,                                                                        5,100                                                                              --   10,100                                                                             --   11,540                                                                             --   11,680                                                                             --   8,540                                                                              --                  Cycles.sup.e                                                                  __________________________________________________________________________     *Not an example of the present invention.                                     .sup.a Percent by weight based on the weight of the resin.                    .sup.b Percent by weight based on the weight of resin plus styrene.           .sup.c Epoxidized soybean oil.                                                .sup.d Cobalt naphthenate (6% Co).                                            .sup.e Cycles to failure.                                                

EXAMPLE 2

A paste concentrate for addition to vinyl ester and unsaturatedpolyester resins is prepared by blending the following:

    ______________________________________                                        styrene               30.8 percent                                            ceresin wax           15.3 percent                                            corn oil              23.1 percent                                            epoxidized soybean oil                                                                              30.8 percent                                                                 100.0 percent                                            ______________________________________                                    

The blending operation is conducted in a 7-gallon (26.5 L) glass vesselusing an air driven stirrer at a temperature of 75° C. When mixture isclear, all wax dissolved, the mixture is allowed to cool to 65° C. to70° C. Gallon (3.8 L) quantities of the mixture are drained into onegallon (3.8 L) cans, which are sealed and shaken until the cans are atroom temperature.

This paste concentrate is employed as an additive to vinyl ester resin Aand polyester resin A and tested for styrene loss. The formulations andresults are given in Table II.

                  TABLE II                                                        ______________________________________                                                   Formulation                                                                   A      B        C        D                                         ______________________________________                                        Resin-Styrene                                                                              100      100      100    100                                     preblend, gms                                                                 Resin,                                                                        Type         VER A    VER A    PER A  PER A                                   gms          55       55       53-57  53-57                                   Styrene,                                                                      gms          45       45       43-47  43-47                                   percent.sup.a                                                                              45       45       43-47  43-47                                   Paste Additive, gms                                                                        1.3      1.3      1.3    1.3                                     percent.sup.b                                                                              1.3      1.3      1.3    1.3                                     Ceresin Wax, gms                                                                           0.2      0.2      0.2    0.2                                     percent.sup.c                                                                              0.2      0.2      0.2    0.2                                     Corn oil, gms                                                                              0.3      0.3      0.3    0.3                                     percent.sup.c                                                                              0.3      0.3      0.3    0.3                                     ESO.sup.d, gms                                                                             0.4      0.4      0.4    0.4                                     percent.sup.c                                                                              0.4      0.4      0.4    0.4                                     Styrene, gms 0.4      0.4      0.4    0.4                                     percent.sup.e                                                                              0.7      0.7      0.7-0.8                                                                              0.7-0.8                                 Temp.,                                                                        °F.   74-76    75       77     76-77                                   °C.   23.3-24.4                                                                              23.9     25     24.4-25                                 Relative Humidity,                                                                         62-70    66       60-63  60-64                                   percent                                                                       Styrene loss 96       86       40     56                                      g/m.sup.2                                                                     ______________________________________                                         .sup.a Percent by weight based on the weight of the resin.                    .sup.b Percent by weight based on the weight of resin plus styrene            excluding the styrene included in the paste additive.                         .sup.c Percent by weight based on the weight of resin plus styrene            including the styrene added via the past additive.                            .sup.d Epoxidized soybean oil.                                                .sup.e Percent by weight based on the weight of the resin.               

What is claimed is:
 1. The article resulting from shaping into a desiredconfiguration and curing one or more plies of a substrate materialsaturated or impregnated with a curable composition comprising (A) atleast one vinyl ester resin or at least one unsaturated polyester resinor a combination thereof; (B) at least one polymerizable, vaporizable,ethylenically unsaturated monomer; (C) a polymerizable, vaporizable,ethylenically unsaturated monomer emission suppression amount of ceresinwas; (D) a drying oil in an amount of from about 0.1 to about 0.70percent by weight based upon the combined weight of resin andpolymerizable, vaporizable, ethylenically unsaturated monomer; (E) anepoxidized drying oil employed in an amount of from about 0.2 to about0.7 percent by weight based upon the combined weight of resin andpolymerizable, vaporizable, ethylenically unsaturated monomer; and (F) acuring amount of a curing agent.
 2. The article of claim 1 wherein saidpolymerizable, vaporizable, ethylenically unsaturated monomer isemployed in an amount of from about 20 to about 60 percent by weightbased upon the combined weight of resin and polymerizable, vaporizable,ethylenically unsaturated monomer, said ceresin wax is employed in anamount of from about 0.15 to about 0.40 percent by weight based upon thecombined weight of resin and polymerizable, vaporizable, ethylenicallyunsaturated monomer.
 3. The article of claim 1 wherein saidpolymerizable, vaporizable, ethylenically unsaturated monomer isemployed in an amount of from about 35 to about 55 percent by weightbased upon the combined weight of resin and polymerizable, vaporizable,ethylenically unsaturated monomer, said ceresin wax is employed in anamount of from about 0.15 to about 0.3 percent by weight based upon thecombined weight of resin and polymerizable, vaporizable, ethylenicallyunsaturated monomer, said drying oil is employed in an amount of fromabout 0.2 to about 0.5 percent by weight based upon the combined weightof resin and polymerizable, vaporizable, ethylenically unsaturatedmonomer, and said epoxidized drying oil is employed in an amount of fromabout 0.3 to about 0.6 percent by weight based upon the combined weightof resin and polymerizable, vaporizable, ethylenically unsaturatedmonomer.
 4. The article of claim 1 wherein said vinyl ester resin is onewhich has been prepared from a diglycidyl ether of bisphenol A andmethacrylic acid, said polymerizable, vaporizable, ethylenicallyunsaturated monomer is styrene and is employed in an amount of fromabout 40 to about 50 percent by weight based upon the combined weight ofresin and polymerizable, vaporizable, ethylenically unsaturated monomer,sad ceresin wax is employed in an amount of from about 0.18 to about0.25 percent by weight based upon the combined weight of resin andpolymerizable, vaporizable, ethylenically unsaturated monomer, saiddrying oil is corn oil and is employed in an amount of from about 0.25to about 0.40 percent by weight based upon the combined weight of resinand polymerizable, vaporizable, ethylenically unsaturated monomer, andsaid epoxidized drying oil is epoxidized soybean oil and is employed inan amount of from about 0.35 to about 0.5 percent by weight based uponthe combined weight of resin and polymerizable, vaporizable,ethylenically unsaturated monomer.